Method for preparing olefin-diene copolymer using transition metal compound containing thiophene-fused cyclopentadienyl ligand

ABSTRACT

The present invention relates to a preparation method for olefin-diene copolymer that comprises polymerizing at least one olefin-based monomer and at least one diene-based monomer in the presence of a catalyst comprising a novel transition metal compound. Using the novel transition metal compound as a catalyst, the preparation method for olefin-diene copolymer according to the present invention can not only acquire high catalytic activity for copolymerization of the olefin and diene monomers to achieve high process efficiency but allow it to easily control the fine-structure characteristics of the copolymer, thereby providing an olefin-diene copolymer having desired properties with ease.

FIELD OF THE INVENTION

The present invention relates to a method for preparing an olefin-dienecopolymer using a transition metal compound containing a thiophene-fusedcyclopentadienyl ligand.

BACKGROUND OF THE INVENTION

Sustainable attempts have been made in the fields of academy andindustry to prepare a polyolefin with desired properties using a varietyof homogenous catalysts since Prof. Kaminsky developed the homogeneousZiegler-Natta catalyst using a Group 4 metallocene compound activatedwith a methylaluminoxane co-catalyst in the late 1970's.

The conventional heterogeneous catalysts in ethylene/α-olefincopolymerization not only provide a low quantity of α-olefinincorporation but cause the α-olefin incorporation to occur primarily inthe polymer chain with low molecular weight only. Contrarily, thehomogenous catalysts in ethylene/α-olefin copolymerization lead toinduce a high quantity of α-olefin incorporation and provide uniformα-olefin distribution.

In contrast to the heterogeneous catalysts, however, the homogenouscatalysts are hard of providing a polymer with high molecular weight.

With low molecular weight, the polymers encounter a limitation indevelopment of their usage, such as being inapplicable to the productsrequired to have high strength. For that reason, the conventionalheterogeneous catalysts have been used in the industrial manufacture ofpolymers, and the usage of the homogeneous catalysts is confined to themanufacture for some grades of polymer.

On the other hand, there has been suggested a technique for preparing anolefin copolymer or an olefin/diene copolymer with desired propertiesusing a variety of metallocene catalysts. However, an excess of thediene monomer is inevitably used due to the characteristic reactivity ofthe diene monomer, only to reduce the polymerization rate and activityof the olefin monomer, making it difficult to control the properties ofthe copolymer.

DISCLOSURE OF INVENTION Technical Problem

It is therefore an object of the present invention to provide a methodfor preparing an olefin-diene copolymer using a catalyst that has a highcatalytic activity for copolymerization of olefin and diene monomers andenables it to control the properties of the copolymer product with ease.

Technical Solution

To achieve the object of the present invention, there is provided amethod for preparing an olefin-diene copolymer that comprisespolymerizing at least one olefin-based monomer and at least onediene-based monomer in the presence of a catalyst comprising atransition metal compound represented by the following formula 1:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ arylC₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen;C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkylC₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; orC₁-C₂₀ silyl with or without an acetal, ketal, or ether group, where R¹and R² can be linked to each other to form a ring; R³ and R⁴ can belinked to each other to form a ring; and at least two of R⁵ to R¹⁰ canbe linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

In the transition metal compound of the formula 1, M is titanium (Ti),zirconium (Zr), or hafnium (Hf); Q¹ and Q² are independently methyl orchlorine; R¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl;and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen.

The catalyst may further comprise at least one co-catalyst compoundselected from the group consisting of compounds represented by thefollowing formula 6, 7, or 8.—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbylradical; and a is an integer of 2 or above.D(R⁷¹)₃  [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical.[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radicalhaving at least one hydrogen atom substituted with a halogen radical, aC₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxyradical.

As for the co-catalyst compound, in the formula 6, R⁶¹ is methyl, ethyl,n-butyl, or isobutyl. In the formula 7, D is aluminum, and R⁷¹ is methylor isobutyl; or D is boron, and R⁷¹ is pentafluorophenyl. In the formula8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is [B(C₆F₅)₄]⁻, and[L]⁺ is [(C₆H₅)₃C]⁺.

The content of the co-catalyst compound is given such that the molarratio of a metal in the co-catalyst compound with respect to one mole ofa transition metal in the transition metal compound of the formula 1 is1:1 to 1:100,000.

Further, the catalyst may comprise the transition metal compound of theformula 1 bound to at least one support selected from the groupconsisting of SiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO,ZnO, BaO, ThO₂, SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃,SiO₂—TiO₂—MgO, bauxite, zeolite, starch, and cyclodextrine.

The olefin-based monomer is at least one selected from the groupconsisting of C₂-C₂₀ α-olefin, C₃-C₂₀ cyclo-olefin, and C₃-C₂₀cyclo-diolefin.

The diene-based monomer is at least one selected from the groupconsisting of C₄-C₂₀ conjugated diene, C₅-C₂₀ aliphatic non-conjugateddiene, C₅-C₂₀ cyclic non-conjugated diene, and C₆-C₂₀ aromaticnon-conjugated diene.

The polymerization step is carried out at a temperature of −50 to 500°C. and a pressure of 1 to 3,000 atm.

Further, the content ratio of the diene-based monomer to theolefin-based monomer polymerized into the olefin-diene copolymer is1:0.1 to 1:10.

Further, the olefin-diene copolymer has a weight average molecularweight of 10,000 to 1,000,000; a molecular weight distribution (Mw/Mn)of 1 to 10; and a density of 0.850 to 0.920 g/ml.

Advantageous Effects

Using a novel transition metal compound as a catalyst, the preparationmethod for olefin-diene copolymer according to the present invention cannot only acquire high catalytic activity for copolymerization of olefinand diene monomers to achieve high efficiency of the process but easilycontrol the fine-structure characteristics of the copolymer, therebyproviding an olefin-diene copolymer having desired properties with ease.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, a description will be given as to a method for preparing anolefin-diene copolymer according to the embodiments of the presentinvention.

In the course of repeated studies on the catalysts for olefinpolymerization, the inventors of the present invention have found out anovel ligand in which an amido ligand is linked to an ortho-phenyleneligand to form a condensed ring, and a 5-membered cyclic pi-ligandlinked to the ortho-phenylene ligand is fused with a heterocyclicthiophene ligand. Also, they have found it out that a transition metalcompound comprising the ligand exhibits higher catalytic activity andprovides a polymer with higher molecular weight than a transition metalcompound not fused with a heterocyclic thiophene ligand.

Particularly, it has been revealed that the use of the transition metalcompound comprising the novel ligand in the preparation of olefin-dienecopolymer makes it easier to control the fine-structure characteristicsof the copolymer and thus allows the preparation of an olefin-dienecopolymer having a high content of the diene co-monomer and highmolecular weight, thereby completing the present invention.

In accordance with one embodiment of the present invention, there isprovided a method for preparing an olefin-diene copolymer that comprisespolymerizing at least one olefin-based monomer and at least onediene-based monomer in the presence of a catalyst comprising atransition metal compound represented by the following formula 1:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ arylC₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen;C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkylC₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; orC₁-C₂₀ silyl with or without an acetal, ketal, or ether group, where R¹and R² can be linked to each other to form a ring; R³ and R⁴ can belinked to each other to form a ring; and at least two of R⁵ to R¹⁰ canbe linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

Firstly, the catalyst used in the preparation method of the presentinvention will be described.

The catalyst comprises a transition metal compound represented by theformula 1.

The transition metal composition of the formula 1 is activated with anunder-mentioned co-catalyst compound to provide activity forpolymerization reaction of olefin.

The transition metal compound of the formula 1 comprises a novel ligandin which an amido ligand is linked to an ortho-phenylene ligand to forma condensed ring, and a 5-membered cyclic pi-ligand linked to theortho-phenylene ligand is fused with a heterocyclic thiophene ligand.Accordingly, the transition metal compound exhibits higher catalyticactivity for olefin-diene copolymerization than the transition metalcompound not fused with a heterocyclic thiophene ligand.

According to the present invention, in the compound of the formula 1,R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ areindependently substituted with a substituent, including acetal, ketal,and ether groups. With such substituents, the transition metal compoundcan be more favored in being supported on the surface of a support.

In the compound of the formula 1, M is preferably titanium (Ti),zirconium (Zr), or hafnium (Hf).

Preferably, Q¹ and Q² are independently halogen or C₁-C₂₀ alkyl. Morepreferably, Q¹ and Q² are independently chlorine or methyl.

R¹, R², R³, R⁴, and R⁵ are independently hydrogen or C₁-C₂₀ alkyl,preferably hydrogen or methyl. More preferably, R¹, R², R³, R⁴, and R⁵are independently hydrogen or methyl, with the provision that at leastone of R³ and R⁴ is methyl; and R⁵ is methyl.

Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independentlyhydrogen.

The transition metal compound of the formula 1 preferably includes theabove-mentioned substituents with a view to controlling the electronicand steric environments around the metal.

On the other hand, the transition metal compound of the formula 1 can beobtained from a precursor compound represented by the following formula2:

In the formula 2, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ are as defined in the formula 1.

In this regard, the precursor compound of the formula 2 may be preparedby a method comprising: (a) reacting a tetrahydroquinoline derivativerepresented by the following formula 3 with alkyl lithium and addingcarbon dioxide to prepare a compound represented by the followingformula 4; and (b) reacting the compound of the formula 4 with alkyllithium, adding a compound represented by the following formula 5, andthen treating with an acid:

In the formulas 3, 4 and 5, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², and R¹³ are as defined in the formula 1.

In the formulas 3, 4 and 5, R¹, R², R³, R⁴, and R⁵ are independentlyhydrogen or C₁-C₂₀ alkyl, preferably hydrogen or methyl. Morepreferably, R¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl,with the provision that at least one of R³ and R⁴ is methyl; and R⁵ ismethyl. Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ areindependently hydrogen. In this manner, the precursor compound isadvantageous in securing easy accessibility and reactivity of a startingmaterial and controlling the electronic and steric environments for thedesired transition metal compound of the formula 1.

The step (a) involves reacting a tetrahydroquinoline derivative of theformula 3 with alkyl lithium and then adding carbon dioxide to form acompound of the formula 4, which process can be achieved by the methodsdisclosed in the known documents (Tetrahedron Lett. 1985, 26, 5935;Tetrahedron 1986, 42, 2571; and J. Chem. SC. Perkin Trans. 1989, 16).

In the step (b), the compound of the formula 4 is reacted with alkyllithium to activate deprotonation and produce an ortho-lithium compound,which is then reacted with a compound of the formula 5 and treated withan acid to obtain a precursor for transition metal compound of theformula 2.

The method of producing an ortho-lithium compound by reaction betweenthe compound of the formula 4 and alkyl lithium can be understood fromthe known documents (Organometallics 2007, 27,6685; and Korean PatentRegistration No. 2008-0065868). In the present invention, theortho-lithium compound is reacted with a compound of the formula 5 andtreated with an acid to produce a precursor for transition metalcompound of the formula 2.

The compound of the formula 5 can be prepared by a variety of knownmethods. For example, the following Scheme 1 can be used to prepare theprecursor for the transition metal compound of the present inventionwith ease in a one-step process, which is economically beneficial byusing inexpensive starting materials (J. Organomet. Chem., 2005,690,4213).

On the other hand, a variety of known methods can be employed tosynthesize the transition metal compound of the formula 1 from theprecursor for transition metal compound represented by the formula 2obtained by the above-stated preparation method. According to oneembodiment of the present invention, 2 equivalents of alkyl lithium isadded to the precursor for transition metal compound of the formula 2 toinduce deprotonation for producing a dilithium compound ofcyclopentadienyl anion and amide anion, and (Q¹)(Q²)MCl₂ is then addedto the dilithium compound to eliminate 2 equivalents of LiCl, therebypreparing the transition metal compound of the formula 1.

According to another embodiment of the present invention, the compoundof the formula 2 is reacted with M(NMe₂)₄ to eliminate 2 equivalents ofHNME₂ and produce a transition metal compound of the formula 1, whereboth Q¹ and Q² are NMe₂. The transition metal compound is then reactedwith Me₃SiCl or Me₂SiCl₂ to replace the NMe₂ ligand with a chlorineligand.

On the other hand, the catalyst used in the preparation method of thepresent invention may further comprise a co-catalyst compound.

The co-catalyst compound is to activate the transition metal compound ofthe formula 1. Thus, any kind of compound can be used as the co-catalystcompound without limitation in its construction, provided that it canactivate the transition metal compound without deteriorating thecatalytic activity of the catalyst of the present invention.

In accordance with one embodiment of the present invention, theco-catalyst compound is preferably at least one selected from the groupconsisting of compounds represented by the following formula 6, 7, or 8:—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbylradical; and a is an integer of 2 or above.D(R⁷¹)₃  [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical.[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radicalhaving at least one hydrogen atom substituted with a halogen radical, aC₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxyradical.

In this regard, the co-catalyst compound of the formula 6 is notspecifically limited in its construction, provided that it isalkylaluminoxane, and may be preferably methylaluminoxane,ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane,decylaluminoxane, etc.

Further, the co-catalyst compound of the formula 7 may betrialkylaluminum (e.g., trimethylaluminum, triethylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum,etc.); dialkylaluminum alkoxide (e.g., dimethylaluminum methoxide,diethylaluminum methoxide, dibutylaluminum methoxide, etc.);dialkylaluminum halide (e.g., dimethylaluminum chloride, diethylaluminumchloride, dibutylaluminum chloride, etc.); alkylaluminum dialkoxide(e.g., methylaluminum dimethoxide, ethylaluminum dimethoxide,butylaluminum dimethoxide, etc.); alkylaluminum dihalide (e.g.,methylaluminum dichloride, ethylaluminum dichloride, butylaluminumdichloride, etc.); trialkyl boron (e.g., trimethyl boron, triethylboron, triisobutyl boron, tripropyl boron, tributyl boron, etc.); ortris-pentafluorophenyl boron.

Further, the co-catalyst compound of the formula 8 may betrimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(4-(t-triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,N,N-dimethylanilinium pentafluorophenoxy tris(pentafluorphenyl)borate,N,N-diethylanilinium tetrakis(pentafluorphenyl)borate,N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethylammonium tetrakis(2,3,5,6-tetrafluorophenyl)borate,N,N-diethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl)borate, and so forth.

The co-catalyst compound of the formula 8 may also be dialkylammonium(e.g., di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate, etc.);trialkylphosphonium (e.g., triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(o-tolylphosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, etc.); dialkyloxonium (e.g.,diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxoniumtetrakis(pentafluororphenyl)borate, di(2,6-dimethylphenyloxoniumtetrakis(pentafluorophenyl)borate, etc.); dialkylsulfonium (e.g.,diphenylsulfonium tetrakis(pentafluorophenyl)borate,di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate,bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate,etc.); or carbonium salts (e.g., tropyliumtetrakis(pentafluorophenyl)borate, triphenylmethylcarbeniumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, etc.).

According to the present invention, in order for the co-catalystcompound to exhibit the enhanced effect of activation, the conditionsare preferably given as follows: in the formula 6, R⁶¹ is methyl, ethyl,n-butyl, or isobutyl; in the formula 7, D is aluminum (Al), and R⁷¹ ismethyl or isobutyl; or D is boron (B), and R⁷¹ is pentafluorophenyl; andin the formula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is[B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.

The added amount of the co-catalyst compound can be determined inconsideration of the added amount of the transition metal compound ofthe formula 1, the required amount of the co-catalyst for sufficientactivation of the transition metal compound, and so forth.

As for the content of the co-catalyst compound, the molar ratio of ametal in the co-catalyst compound with respect to one mole of atransition metal in the transition metal compound of the formula 1 is1:1 to 1:100,000, preferably 1:1 to 1:10,000, more preferably 1:1 to1:5,000.

More specifically, the co-catalyst of the formula 6 may be used at amolar ratio of 1:1 to 1:100,000, preferably 1:5 to 1:50,000, morepreferably 1:10 to 1:20,000 with respect to the transition metalcompound of the formula 1.

Further, the co-catalyst compound of the formula 7, where D is boron(B), may be used at a molar ratio of 1:1 to 1:100, preferably 1:1 to1:10, more preferably 1:1 to 1:3, with respect to the transition metalcompound of the formula 1.

Although dependent upon the amount of water in the polymerizationsystem, the co-catalyst compound of the formula 7, where D is aluminum(Al), may be used at a molar ratio of 1:1 to 1:1,000, preferably 1:1 to1:500, more preferably 1:1 to 1:100, with respect to the transitionmetal compound of the formula 1.

Further, the co-catalyst of the formula 8 may be used at a molar ratioof 1:1 to 1:100, preferably 1:1 to 1:10, more preferably 1:1 to 1:4 withrespect to the transition metal compound of the formula 1.

On the other hand, the catalyst used in the preparation method of thepresent invention may be a catalyst in which the transition metalcompound of the formula 1 or a combination of the transition metalcompound and the co-catalyst compound is bound to the surface of asupport.

In this regard, the support as used herein may be any kind of inorganicor organic support used in the preparation of a catalyst in the relatedart of the present invention.

According to one embodiment of the present invention, the support may beSiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂,SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃, SiO₂—TiO₂—MgO,bauxite, zeolite, starch, cyclodextrine, or synthetic polymer.

Preferably, the support includes hydroxyl groups on its surface and maybe at least one selected from the group consisting of silica,silica-alumina, and silica-magnesia.

The supporting method for the transition metal compound and theco-catalyst compound on a support may include: a method of directlysupporting the transition metal compound on a dehydrated support; amethod of pre-treating the support with the co-catalyst compound andthen adding the transition metal compound; a method of supporting thetransition metal compound on a support and then adding the co-catalystfor after-treatment of the support; or a method of reacting thetransition metal compound with the co-catalyst compound and then addinga support.

According to one embodiment of the present invention, the solvent asused in the supporting method is, for example, aliphatichydrocarbon-based solvents (e.g., pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, etc.); aromatic hydrocarbon-basedsolvents (e.g., benzene, monochlorobenzene, dichlorobenzene,trichlorobenzene, toluene, etc.); halogenated aliphatichydrocarbon-based solvents (e.g., dichloromethane, trichloromethane,dichloroethane, trichloroethane, etc.); or mixtures thereof.

In terms of the efficiency of the process for supporting the transitionmetal compound and the co-catalyst compound on a support, the supportingprocess may be preferably carried out at a temperature of −70 to 200°C., preferably −50 to 150° C., more preferably 0 to 100° C.

The preparation method for olefin-diene copolymer according to thepresent invention may comprise polymerizing at least one olefin-basedmonomer and at least one diene-based monomer in the presence of theafore-mentioned catalyst.

In this regard, the olefin and diene monomers are not specificallylimited and may include any kind of olefin and diene monomers generallyused in the related art of the present invention.

According to one embodiment of the present invention, the olefin-basedmonomer is at least one selected from the group consisting of C₂-C₂₀α-olefin, C₃-C₂₀ cyclo-olefin, C₃-C₂₀ cyclo-diolefin, and substituted orunsubstituted styrene.

Preferably, the olefin-based monomer may be C₂-C₂₀ α-olefin, includingethylene, propylene, 1-butene, 1-pentene, or 1-hexene; C₃-C₂₀cyclo-olefin or cyclodiolefin, including cyclopentene, cyclohexene,cyclopentadiene, cyclohexadiene, norbornene, or methyl-2-norbornene;substituted styrene having a C₁-C₁₀ alkyl, alkoxy, halogen, amine,silyl, or haloalkyl group linked to styrene or phenyl ring of styrene;or mixtures thereof.

Further, the diene-based monomer is at least one selected from the groupconsisting of C₄-C₂₀ conjugated diene, C₅-C₂₀ aliphatic non-conjugateddiene, C₅-C₂₀ cyclic non-conjugated diene, and C₆-C₂₀ aromaticnon-conjugated diene.

Preferably, the diene-based monomer may be at least one selected fromthe group consisting of C₄-C₂₀ conjugated diene-based monomers (e.g.,butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,2-dimethyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene,1-ethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene,4-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene,2,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, etc.); C₅-C₂₀aliphatic non-conjugated diene-based monomers (e.g., 1,4-pentadiene,1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-heptadiene,6-methyl-1,5-heptadiene, 1,6-octadiene, 1,7-octadiene,7-methyl-1,6-octadiene, 1,13-tetradicadiene, 1,19-icosadiene, etc.);C₅-C₂₀ cyclic non-conjugated diene-based monomers (e.g.,1,4-cyclohexadiene, bicyclo[2,2,2]hept-2,5-diene,5-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-vinyl-2-norbornene, bicyclo[2,2,2]oct-2,5-diene,4-vinylcyclohex-1-ene, bicyclo[2,2,1]hept-2,5-diene, bicyclopentadiene,methyltetrahydroindene, 5-allylbicyclo[2,2,1]hept-2-ene,1,5-cyclooctadiene, etc.); and C₆-C₂₀ aromatic non-conjugateddiene-based monomers (e.g., 1,4-diallylbenzene, 4-allyl-1H-indene,etc.).

In addition to the above-mentioned diene-based monomers, the presentinvention may use C₆-C₂₀ triene-based monomers, such as2,3-diisoprophenylidene-5-norbornene,2-ethylidene-3-isopropylidene-5-norbornene, 2-propyl-2,5-norbornadiene,1,3,7-octatriene, 1,4,9-decatriene, etc.

The polymerization step may be carried out by way of slurry, solution,gas, or bulk polymerization.

In the polymerization step conducted in the solution or slurry phase,the solvent or the olefin-based monomer itself can be used as a medium.

The solvent as used in the polymerization step may be aliphatichydrocarbon solvents (e.g., butane, isobutane, pentane, hexane, heptane,octane, nonane, decane, undecane, dodecane, cyclopentane,methylcyclopentane, cyclohexane, etc.); aromatic hydrocarbon-basedsolvents (e.g., benzene, monochlorobenzene, dichlorobenzene,trichlorobenzene, toluene, xylene, chlorobenzene, etc.); halogenatedaliphatic hydrocarbon solvents (e.g., dichloromethane, trichloromethane,chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane,etc.); or mixtures thereof.

In the polymerization step, the added amount of the catalyst is notspecifically limited and may be determined within a range allowing asufficient polymerization reaction of the monomer depending on whetherthe process is carried out by way of slurry, solution, gas, or bulkpolymerization.

According to the present invention, the added amount of the catalyst is10⁻⁸ to 1 mol/L, preferably 10⁻⁷ to 10⁻¹ mol/L, more preferably 10⁻⁷ to10⁻² mol/L, based on the concentration of the central metal of thetransition metal compound per unit volume (L) of the monomer.

Further, the polymerization step may be carried out by way of the batchtype, semi-continuous type, or continuous type reaction.

The temperature and pressure conditions for the polymerization step arenot specifically limited and may be determined in consideration of theefficiency of the polymerization reaction depending on the types of thereaction and the reactor used.

According to the present invention, the polymerization step may becarried out at a temperature of −50 to 500° C., preferably 0 to 400° C.,more preferably 0 to 300° C. Further, the polymerization step may becarried out under the pressure of 1 to 3,000 atm, preferably 1 to 1,000atm, more preferably 1 to 500 atm.

On the other hand, the preparation method for olefin-diene copolymeraccording to the present invention allows it to control thefine-structure characteristics of the copolymer with ease by using theafore-mentioned catalyst, thereby providing an olefin-diene copolymerwith a high content of the diene co-monomer, high molecular weight, anddesired properties.

In other words, the content ratio of the diene-based monomer to theolefin-based monomer in the olefin-diene copolymer may be 1:0.1 to 1:10,preferably 1:0.1 to 1:5, more preferably 1:0.1 to 1:1.

Further, the olefin-diene copolymer may have a weight average molecularweight (Mw) of 10,000 to 1,000,000, preferably 50,000 to 800,000, morepreferably 50,000 to 500,000.

The olefin-diene copolymer may have a molecular weight distribution(Mw/Mn) of 1 to 10, preferably 1.5 to 8, more preferably 1.5 to 6.

The olefin-diene copolymer may have a density of 0.085 to 0.920 g/ml.

On the other hand, the preparation method for copolymer according to thepresent invention may further comprise, in addition to theafore-mentioned steps, a step known to those skilled in the art beforeor after the afore-mentioned steps, which are not given to limit thepreparation method of the present invention.

Hereinafter, a detailed description will be given as to the presentinvention in accordance with the preferred embodiments, which are givenby way of illustration only and not intended to limit the scope of thepresent invention.

The following synthesis procedures (i) and (ii) for the precursor andthe transition metal compound were performed in the atmosphere of inertgas, such as nitrogen or argon, according to the following Schemes 2 and3, using the standard Schlenk and glove box techniques.

The individual compounds in the Scheme 2 come in different substituents.The substituents are presented in the table given below thecorresponding compound (for example, the compound D-2 denotes a compoundhaving a hydrogen atom for R^(a) and a methyl group for R^(b) andR^(c)).

In the Scheme 2, the compound C (C-1, C-2, or C-3) was synthesized by aknown method (J. Organomet. Chem., 2005, 690, 4213).

(i) Synthesis of Precursor Example i-1 Synthesis of Precursor D-1

A Schlenk flask containing 1,2,3,4-tetrahydroquinoline (1.00 g, 7.51mmol) and diethyl ether (16 ml) was cooled down in a cold bath at −78°C. and stirred while n-butyl lithium (3.0 mL, 7.5 mmol, 2.5 M hexanesolution) was slowly added under the nitrogen atmosphere. After one-houragitation at −78° C., the flask was gradually warmed up to the roomtemperature. A light yellowish solid precipitated, and the butane gaswas removed through a bubbler. The flask was cooled down back to −78° C.and supplied with carbon dioxide. Upon injection of carbon dioxide, theslurry-type solution turned to a clear homogenous solution. Afterone-hour agitation at −78° C., the flask was gradually warmed up −20° C.while the extra carbon dioxide was removed through the bubbler to remaina white solid as a precipitate.

Tetrahydrofuran (0.60 g, 8.3 mmol) and t-butyl lithium (4.9 mL, 8.3mmol, 1.7 M pentane solution) were sequentially added at −20° C. in thenitrogen atmosphere, and the flask was agitated for about 2 hours.Subsequently, a tetrahydrofuran solution (19 mL) containing lithiumchloride and the compound C-1 (1.06 g, 6.38 mmol) was added in thenitrogen atmosphere. The flask was agitated at −20° C. for one hour andthen gradually warmed up to the room temperature. After one-houragitation at the room temperature, water (15 mL) was added to terminatethe reaction. The solution was moved to a separatory funnel to extractthe organic phase. The extracted organic phase was put in a separatoryfunnel, and then hydrochloric acid (2 N, 40 mL) was added. After shakingup the solution for about 2 minutes, an aqueous solution of sodiumhydrocarbonate (60 mL) was slowly added to neutralize the solution. Theorganic phase was separated and removed of water with anhydrousmagnesium sulfate to eliminate the solvent and yield a sticky product.The product thus obtained was purified by the silica gel columnchromatography using a mixed solvent of hexane and ethylacetate (v/v,50:1) to yield 77.2 mg of the desired compound (43% yield).

In the ¹H NMR spectrum of the final product, there was observed a set oftwo signals at ratio of 1:1, resulting from the difficulty of rotatingabout the carbon-carbon bond (marked as a thick line in the Scheme 2)between phenylene and cyclopentadiene. In the following ¹³C NMRspectrum, the values in parenthesis are chemical shift values split dueto the difficulty of rotation.

¹H NMR (C₆D₆): δ 7.22 and 7.17 (br d, J=7.2 Hz, 1H), 6.88 (s, 2H), 6.93(d, J=7.2 Hz, 1H), 6.73 (br t, J=7.2 Hz, 1H), 3.84 and 3.80 (s, 1H, NH),3.09 and 2.98 (q, J=8.0 Hz, 1H, CHMe), 2.90-2.75 (br, 2H, CH₂),2.65-2.55 (br, 2H, CH₂), 1.87 (s, 3H, CH₃), 1.70-1.50 (m, 2H, CH₂), 1.16(d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.64 (151.60), 147.74 (147.61), 146.68, 143.06,132.60, 132.30, 129.85, 125.02, 121.85, 121.72, 119.74, 116.87, 45.86,42.54, 28.39, 22.89, 16.32, 14.21 ppm.

Example i-2 Synthesis of Precursor D-2

The procedures were performed in the same manner as described in Examplei-1, excepting that the compound C-2 was used rather than the compoundC-1 to synthesize the precursor compound D-2. The yield was 53%.

In the ¹H NMR spectrum of the final product, there was observed a set oftwo signals at ratio of 1:1, resulting from the difficulty of rotatingabout the carbon-carbon bond (marked as a thick line in the Scheme 2)between phenylene and cyclopentadiene.

¹H NMR (C₆D₆): δ 7.23 (d, J=7.2 Hz, 1H), 6.93 (d, J=7.2 Hz, 1H), 6.74(br t, J=7.2 Hz, 1H), 4.00 and 3.93 (s, 1H, NH), 3.05 (br q, J=8.0 Hz,1H, CHMe), 3.00-2.80 (br, 2H, CH₂), 2.70-2.50 (br, 2H, CH₂), 2.16 (s,3H, CH₃), 2.04 (br s, 3H, CH₃), 1.91 (s, 3H, CH₃), 1.75-1.50 (m, 2H,CH₂), 1.21 (d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.60 (151.43), 145.56 (145.36), 143.08, 141.43,132.90, 132.68, 132.43, 129.70, 121.63, 120.01, 116.77, 46.13, 42.58,28.42, 22.97, 15.06, 14.19, 14.08, 12.70 ppm.

Example i-3 Synthesis of Precursor D-3

The procedures were performed in the same manner as described in Examplei-1, excepting that tetrahydroquinaldine was used rather than1,2,3,4-tetrahydroquinoline to synthesize the precursor compound D-3.The yield was 63%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 2) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.33, 7.29, 7.22, and 7.17 (d, J=7.2 Hz, 1H), 6.97 (d,J=7.2 Hz, 1H), 6.88 (s, 2H), 6.80-6.70 (m, 1H), 3.93 and 3.86 (s, 1H,NH), 3.20-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.50 (m, 2H, CH₂), 1.91, 1.89,and 1.86 (s, 3H, CH₃), 1.67-1.50 (m, 1H, CH₂), 1.50-1.33 (m, 1H, CH₂),1.18, 1.16, and 1.14 (s, 3H, CH₃), 0.86, 0.85, and 0.80 (d, J=8.0 Hz,3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.67, 147.68 (147.56, 147.38), 147.06 (146.83, 146.28,146.10), 143.01 (142.88), 132.99 (132.59), 132.36 (131.92), 129.69,125.26 (125.08, 124.92, 124.83), 122.03, 121.69 (121.60, 121.28), 119.74(119.68, 119.46), 117.13 (117.07, 116.79, 116.72), 47.90 (47.73), 46.04(45.85), 31.00 (30.92, 30.50), 28.00 (27.83, 27.64), 23.25 (23.00),16.38 (16.30), 14.63 (14.52, 14.18) ppm.

Example i-4 Synthesis of Precursor D-4

The procedures were performed in the same manner as described in Examplei-1, excepting that the compound C-2 and tetrahydroquinaldine were usedrather than the compound C-1 and 1,2,3,4-tetrahydroquinoline tosynthesize the precursor compound D-4. The yield was 63%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 2) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.32, 7.30, 7.22, and 7.19 (d, J=7.2 Hz, 1H), 6.97 (d,J=7.2 Hz, 1H), 6.85-6.65 (m, 1H), 4.10-3.90 (s, 1H, NH), 3.30-2.85 (m,2H, NCHMe, CHMe), 2.85-2.50 (m, 2H, CH₂), 2.15 (s, 3H, CH₃), 2.02 (s,3H, CH₃), 1.94, 1.92, and 1.91 (s, 3H, CH₃), 1.65-1.50 (m, 1H, CH₂),1.50-1.33 (m, 1H, CH₂), 1.22, 1.21, 1.20, and 1.19 (s, 3H, CH₃),1.10-0.75 (m, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.67 (151.57), 145.58 (145.33, 145.20), 143.10(143.00, 142.89), 141.62 (141.12), 134.08 (133.04), 132.84 (132.70,136.60), 132.50 (132.08), 129.54, 121.52 (121.16), 119.96 (119.71),117.04 (116.71), 47.90 (47.78), 46.29 (46.10), 31.05 (30.53), 28.02(28.67), 23.37 (23.07), 15.22 (15.04), 14.87 (14.02, 14.21), 12.72(12.67) ppm.

Example i-5 Synthesis of Precursor D-5

The procedures were performed in the same manner as described in Examplei-1, excepting that the compound C-3 and tetrahydroquinaldine were usedrather than the compound C-1 and 1,2,3,4-tetrahydroquinoline tosynthesize the precursor compound D-5. The yield was 48%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 2) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.32, 7.29, 7.22 and 7.18 (d, J=7.2 Hz, 1H), 6.96 (d,J=7.2 Hz, 1H), 6.84-6.68 (m, 1H), 6.60 (d, J=7.2 Hz, 1H), 4.00-3.92 (s,1H, NH), 3.30-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.55 (m, 2H, CH₂), 2.27(s, 3H, CH₃), 1.94, 1.91 and 1.89 (s, 3H, CH₃), 1.65-1.54 (m, 1H, CH₂),1.54-1.38 (m, 1H, CH₂), 1.23, 1.22, and 1.20 (s, 3H, CH₃), 1.00-0.75 (m,3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.51, 145.80, 145.64, 145.45, 144.40, 144.22, 143.76,143.03, 142.91, 139.78, 139.69, 139.52, 133.12, 132.74, 132.52, 132.11,129.59, 121.52, 121.19, 120.75, 120.47, 119.87, 119.69, 116.99, 116.76,47.90, 47.77, 46.43, 46.23, 32.55, 30.98, 30.51, 27.95, 27.67, 23.67,23.31, 23.06, 16.52, 15.01, 14.44, 14.05 ppm.

(ii) Synthesis of Transition Metal Compound Example ii-1 Synthesis ofTransition Metal Compound E-1

In a dry box, the compound D-1 (0.10 g, 0.36 mmol) synthesized inExample i-1 and dimethyl ether were put into a round-bottomed flask andcooled down to −30° C. N-butyl lithium (2.5 M hexane solution, 0.2 g,0.71 mmol) was gradually added to the flask under agitation to activatethe reaction at −30° C. for 2 hours. Warmed up to the room temperature,the flask was agitated for more 3 hours for the reaction. After cooleddown back to −30° C., to the flask were added methyl lithium (1.6 Mdiethyl ether solution, 0.33 g, 0.71 mmol) and then TiCl₄.DME (DME:dimethoxyethane, 0.10 g, 0.36 mmol). The flask, while warmed up to theroom temperature, was agitated for 3 hours and then removed of thesolvent using a vacuum line. Pentane was used to extract the compound.The removal of the solvent produced 0.085 g of the final compound as abrownish powder (60% yield).

¹H NMR (C₆D₆): δ 7.09 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81(t, J=7.2 Hz, 1H), 6.74 (s, 2H), 4.55 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.38(dt, J=14, 5.2 Hz, 1H, NCH₂), 2.50-2.30 (m, 2H, CH₂), 2.20 (s, 3H), 1.68(s, 3H), 1.68 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H, TiMe), 0.38 (s, 3H,TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.46, 142.43, 140.10, 133.03, 130.41, 129.78,127.57, 127.34, 121.37, 120.54, 120.51, 120.34, 112.52, 58.50, 53.73,49.11, 27.59, 23.27, 13.19, 13.14 ppm.

Example ii-2 Synthesis of Transition Metal Compound E-2

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-2 was used rather than the compoundD-1 to synthesize the transition metal compound E-2. The yield was 53%.

¹H NMR (C₆D₆): δ 7.10 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81(t, J=7.2 Hz, 1H), 4.58 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.42 (dt, J=14,5.2 Hz, 1H, NCH₂), 2.50-2.38 (m, 2H, CH₂), 2.32 (s, 3H), 2.11 (s, 3H),2.00 (s, 3H), 1.71 (s, 3H), 1.67 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H,TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.58, 141.36, 138.41, 137.20, 132.96, 129.70,127.53, 127.39, 126.87, 121.48, 120.37, 120.30, 113.23, 56.50, 53.13,49.03, 27.64, 23.34, 14.21, 13.40, 12.99, 12.94 ppm. Anal. Calc.(C₂₂H₂₇NSTi): C, 68.56; H, 7.06; N, 3.63. Found: C, 68.35H, 7.37 N,3.34%.

Example ii-3 Synthesis of Transition Metal Compound E-3

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-3 was used rather than the compoundD-1 to synthesize the transition metal compound E-3. The yield was 51%.The final product was identified as a 1:1 mixture (the direction of thethiophene cyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.11 and 7.08 (d, J=7.2 Hz, 1H), 6.96 and 6.95 (d,J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 6.77 and 6.76 (d, J=7.2Hz, 1H), 6.74 and 6.73 (d, J=7.2 Hz, 1H), 5.42 (m, 1H, NCH), 2.75-2.60(m, 1H, CH₂), 2.45-2.25 (m, 1H, CH₂), 2.24 and 2.18 (s, 3H), 1.73 and1.63 (s, 3H), 1.85-1.50 (m, 2H, CH₂), 1.17 and 1.15 (d, J=4.8 Hz, 3H),0.76 and 0.70 (s, 3H, TiMe), 0.42 and 0.32 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 159.58, 159.28, 141.88, 141.00, 139.63, 138.98,134.45, 130.85, 130.50, 129.59, 129.50, 129.47, 127.23, 127.20, 127.17,127.11, 120.77, 120.70, 120.40, 120.00, 119.96, 119.91, 118.76, 118.57,113.90, 110.48, 59.61, 56.42, 55.75, 51.96, 50.11, 49.98, 27.41, 27.11,21.89, 20.09, 19.67, 12.94, 12.91, 12.65 ppm.

Example ii-4 Synthesis of Transition Metal Compound E-4

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-4 was used rather than the compoundD-1 to synthesize the transition metal compound E-4. The yield was 57%.The final product was identified as a 1:1 mixture (the direction of thethiophene cyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.12 and 7.10 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d,J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 5.45 (m, 1H, NCH),2.75-2.60 (m, 1H, CH₂), 2.45-2.20 (m, 1H, CH₂), 2.34 and 2.30 (s, 3H),2.10 (s, 3H), 1.97 (s, 3H), 1.75 and 1.66 (s, 3H), 1.85-1.50 (m, 2H,CH₂), 1.20 (d, J=6.8 Hz, 3H), 0.76 and 0.72 (s, 3H, TiMe), 0.44 and 0.35(s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 160.13, 159.86, 141.33, 140.46, 138.39, 137.67,136.74, 134.83, 131.48, 129.90, 129.78, 127.69, 127.65, 127.60, 127.45,126.87, 126.81, 121.34, 121.23, 120.21, 120.15, 119.15, 118.93, 114.77,111.60, 57.54, 55.55, 55.23, 51.73, 50.43, 50.36, 27.83, 27.67, 22.37,22.31, 20.53, 20.26, 14.29, 13.51, 13.42, 13.06, 12.80 ppm.

Example ii-5 Synthesis of Transition Metal Compound E-5

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-5 was used rather than the compoundD-1 to synthesize the transition metal compound E-5. The yield was 57%.The final product was identified as a 1:1 mixture (the direction of thethiophene cyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.12 and 7.09 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d,J=7.2 Hz, 1H), 6.82 and 6.80 (t, J=7.2 Hz, 1H), 6.47 and 6.46 (d, J=7.2Hz, 1H), 6.45 and 6.44 (d, J=7.2 Hz, 1H), 5.44 (m, 1H, NCH), 2.76-2.60(m, 1H, CH₂), 2.44-2.18 (m, 1H, CH₂), 2.28 and 2.22 (s, 3H), 2.09 (s,3H), 1.74 and 1.65 (s, 3H), 1.88-1.48 (m, 2H, CH₂), 1.20 and 1.18 (d,J=7.2 Hz, 3H), 0.77 and 0.71 (s, 3H, TiMe), 0.49 and 0.40 (s, 3H, TiMe)ppm.

¹³C{¹H} NMR (C₆D₆): 159.83, 159.52, 145.93, 144.90, 140.78, 139.93,139.21, 138.86, 135.26, 131.56, 129.69, 129.57, 127.50, 127.46, 127.38,127.24, 121.29, 121.16, 120.05, 119.96, 118.90, 118.74, 117.99, 117.74,113.87, 110.38, 57.91, 55.31, 54.87, 51.68, 50.27, 50.12, 34.77, 27.58,27.27, 23.10, 22.05, 20.31, 19.90, 16.66, 14.70, 13.11, 12.98, 12.68ppm.

Example ii-6 Synthesis of Transition Metal Compound E-6

The transition metal compound E-6 was synthesized according to thefollowing Scheme 3.

Methyl lithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) wasadded dropwise to a diethyl ether solution (10 mL) containing thecompound D-4 (0.58 g, 1.79 mmol). The solution was agitated overnight atthe room temperature and cooled down to −30° C. Then, Ti(NMe₂)₂Cl₂ (0.37g, 1.79 mmol) was added at once. After 3-hour agitation, the solutionwas removed of all the solvent with a vacuum pump. The solid thusobtained was dissolved in toluene (8 mL), and Me₂SiCl₂ (1.16 g, 8.96mmol) was added to the solution. The solution was agitated at 80° C. for3 days and removed of the solvent with a vacuum pump to obtain a reddishsolid compound (0.59 g, 75% yield). The ¹H NMR spectrum showed theexistence of two stereo-structural compounds at ratio of 2:1.

¹H NMR (C₆D₆): δ 7.10 (t, J=4.4 Hz, 1H), 6.90 (d, J=4.4 Hz, 2H), 5.27and 5.22 (m, 1H, NCH), 2.54-2.38 (m, 1H, CH₂), 2.20-2.08 (m, 1H, CH₂),2.36 and 2.35 (s, 3H), 2.05 and 2.03 (s, 3H), 1.94 and 1.93 (s, 3H),1.89 and 1.84 (s, 3H), 1.72-1.58 (m, 2H, CH₂), 1.36-1.28 (m, 2H, CH₂),1.17 and 1.14 (d, J=6.4, 3H, CH₃) ppm.

¹³C{¹H} NMR (C₆D₆): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12,130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87, 54.18, 26.48,21.74, 17.28, 14.46, 14.28, 13.80, 13.27 ppm.

(iii) Preparation of Olefin-Diene Copolymer

The individual polymerization reaction was carried out in an airtightautoclave using required amounts of a solvent, a co-catalyst compound,and monomers, and then a transition metal compound.

After completion of the polymerization, the polymer product was measuredin regard to the molecular weight and the molecular weight distributionby the GPC (Gel Permeation Chromatography) (instrument: PL-GPC220supplied by Agilent), and the melting point by the DSC (DifferentialScanning Calorimetry) (instrument: Q200 supplied by TA Instruments).

The monomer content in the polymer was analyzed through FT-IR (FourierTransform Infrared Spectrometer) (instrument: MAGNA-IR550 Spectrometersupplied by Nicolet) and ¹³C NMR (instrument: Avance 400 Spectrometersupplied by Bruker).

The measurement results are presented in Table 1.

Example iii-1

An autoclave (capacity: 2 L, stainless steel) was purged with nitrogenat the room temperature and filled with 950 ml of toluene. Then, about10 ml of methylaluminoxane (a solution containing 10 wt. % ofmethylaluminoxane in toluene, 15 mmol of Al, as supplied by Albemarle)and 50 ml of 1,7-octadiene co-monomer were added in sequence.Subsequently, a solution (2 ml, 7.5 μmol) of the transition metalcompound E-6 of Example 11-6 dissolved in toluene was added to theautoclave.

The autoclave was warmed up to 70° C., provided with ethylene gas andmaintained at the total pressure of 7.2 bar to allow a polymerizationreaction for 30 minutes.

After completion of the polymerization reaction, the resultant solutionwas cooled down to the room temperature and removed of the extraethylene gas. Subsequently, the copolymer powder dispersed in thesolvent was filtered out and dried out in a vacuum oven at 80° C. for atleast 15 hours to yield an ethylene-1,7-octadiene copolymer (28.7 g).

Example iii-2

The procedures were performed in the same manner as described in Exampleiii-1, excepting that 100 g of propylene were used rather than ethyleneas an olefin-based monomer, to yield a propylene-1,7-octadiene copolymer(19.4 g).

Example iii-3

The procedures were performed in the same manner as described in Exampleiii-1, excepting that 50 g of ethylene and 50 g of propylene were usedas olefin-based monomers, to yield an ethylene-propylene-1,7-octadienecopolymer (15.9 g).

Example iii-4

The procedures were performed in the same manner as described in Exampleiii-1, excepting that 50 g of ethylene and 50 g of propylene were usedas olefin-based monomers, with dicyclopentdiene being used rather than1,7-octadiene, to yield an ethylene-propylene-dicyclopentadienecopolymer (54.3 g).

Example iii-5

The procedures were performed in the same manner as described in Exampleiii-1, excepting that 50 g of ethylene and 50 g of propylene were usedas olefin-based monomers, with 5-vinyl-2-norbornene being used ratherthan 1,7-octadiene, to yield an ethylene-propylene-5-vinyl-2-norbornenecopolymer (10.0 g).

Example iii-6

The procedures were performed in the same manner as described in Exampleiii-1, excepting that 20 g of ethylene, 20 g of propylene, and5-vinyl-2-norbornene rather than 1,7-octadiene were used at apolymerization temperature of 180° C., to yield anethylene-propylene-5-vinyl-2-norbornene copolymer (6.0 g).

Comparative Example iii-1

The procedures were performed in the same manner as described in Exampleiii-1, excepting that bisindenylzirconium dichloride (Ind₂ZrCl₂,supplied by Strem) was used rather than the transition metal compoundE-6, to yield an ethylene-1,7-octadiene copolymer (23.0 g).

Comparative Example iii-2

The procedures were performed in the same manner as described in Exampleiii-5, excepting that bisindenylzirconium dichloride (Ind₂ZrCl₂,supplied by Strem) was used rather than the transition metal compoundE-6 to yield an ethylene-propylene-5-vinyl-2-norbornene copolymer (7.0g).

TABLE 1 Comparative Example Example iii-1 iii-2 iii-3 iii-4 iii-5 iii-6iii-1 iii-2 Catalytic activity 7.6 5.2 4.3 10.9 2.7 2.5 6.1 1.9 (kg-PE)/(mmol-Metal) (hour) Mw (×10³) 90 403 292 391 220 185 50 132 Molecularweight 1.93 5.30 5.42 3.09 3.55 2.97 2.69 3.98 distribution (Mw/Mn)Melting point (° C.) 79.2 N.D. 20.7 87.9 35.2 61.0 112.3 63.9 Glasstransition −22.4 −2.6 −53.0 −26.4 −35.4 −20.3 −18.2 −12.0 temperature (°C.) Density (g/ml) 0.876 0.874 0.879 0.880 0.860 0.863 0.882 0.875Content C2 74.4 0 60.5 67.3 75 78 87.2 80 (wt %) C3 0 87.4 31.5 22.7 1819 0 19 C4 25.6 12.6 8.0 10.0 7 3 12.8 1 (Note: N.D.—No melting pointdue to the characteristic property of the polymer)

As can be seen from Table 1, it was possible to prepare an olefin-dienecopolymer with higher content of the co-monomer and higher molecularweight by using the catalyst of the present invention as in Examplesiii-1 to iii-6 rather than using the conventional transition metalcompound as in Comparative Example iii-1 and iii-2.

The invention claimed is:
 1. A method for preparing an olefin-dienecopolymer, comprising: polymerizing at least one olefin-based monomerand at least one diene-based monomer in the presence of a catalystcomprising a transition metal compound represented by the followingformula 1:

wherein M is a Group 4 transition metal; Q¹ and Q² are independently ahalogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aryl,C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ aryl C₁-C₂₀ alkyl, C₁-C₂₀ alkylamido,C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene; R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, and R¹⁰ are independently hydrogen; C₁-C₂₀ alkyl with or without anacetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal,ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without anacetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or withoutan acetal, ketal, or ether group; or C₁-C₂ silyl with or without anacetal, ketal, or ether group, wherein R¹ and R² can be linked to eachother to form a ring; R³ and R⁴ can be linked to each other to form aring; and at least two of R⁵ to R¹⁰ can be linked to each other to forma ring; and R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkylwith or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl withor without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkylwith or without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, wherein R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.
 2. The method as claimed in claim 1, wherein M istitanium (Ti), zirconium (Zr), or hafnium (Hf); Q¹ and Q² areindependently methyl or chlorine; R¹, R², R³, R⁴, and R⁵ areindependently hydrogen or methyl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ are independently hydrogen.
 3. The method as claimed in claim 2,wherein at least one of R³ and R⁴ is methyl; and R⁵ is methyl.
 4. Themethod as claimed in claim 1, wherein the catalyst further comprises atleast one co-catalyst compound selected from the group consisting ofcompounds represented by the following formula 6, 7, or 8:—[Al(R⁶¹)—O]_(a)—  [Formula 6] wherein R⁶¹ is independently a halogenradical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀hydrocarbyl radical; and a is an integer of 2 or above,D(R⁷¹)₃  [Formula 7] wherein D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical,[L-H]⁺[Z(A)₄] or [L]⁺[Z(A)₄]⁻  [Formula 8] wherein L is a neutral orcationic Lewis acid; Z is a Group 13 element; and A is independently aC₆-C₂₀ aryl or C₁-C₂₀ alkyl radical having at least one hydrogen atomsubstituted with a halogen radical, a C₁-C₂₀ hydrocarbyl radical, aC₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxy radical.
 5. The method asclaimed in claim 4, wherein in the formula 6, R⁶¹ is methyl, ethyl,n-butyl, or isobutyl; in the formula 7, D is aluminum, and R⁷¹ is methylor isobutyl; or D is boron, and R⁷¹ is pentafluorophenyl; and in theformula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is[B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.
 6. The method as claimed in claim4, wherein the content of the co-catalyst compound is given such thatthe molar ratio of a metal in the co-catalyst compound with respect toone mole of a transition metal in the transition metal compound of theformula 1 is 1:1 to 1:100,000.
 7. The method as claimed in claim 1,wherein the catalyst comprises the transition metal compound of theformula 1, wherein the transition metal compound is bound to at leastone support selected from the group consisting of SiO₂, Al₂O₃, MgO,MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, SiO₂—Al₂O₃,SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃, SiO₂—TiO₂—MgO, bauxite,zeolite, starch, and cyclodextrine.
 8. The method as claimed in claim 1,wherein the olefin-based monomer is at least one selected from the groupconsisting of C₂-C₂₀ α-olefin, C₃-C₂₀ cyclo-olefin, and C₃-C₂₀cyclo-diolefin.
 9. The method as claimed in claim 1, wherein thediene-based monomer is at least one selected from the group consistingof C₄-C₂₀ conjugated diene, C₅-C₂₀ aliphatic non-conjugated diene,C₅-C₂₀ cyclic non-conjugated diene, and C₆-C₂₀ aromatic non-conjugateddiene.
 10. The method as claimed in claim 1, wherein the polymerizationstep is carried out at a temperature of −50 to 500° C. and a pressure of1 to 3,000 atm.
 11. The method as claimed in claim 1, wherein thecontent ratio of the diene-based monomer to the olefin-based monomerpolymerized into the olefin-diene copolymer is 1:0.1 to 1:10.
 12. Themethod as claimed in claim 1, wherein the olefin-diene copolymer has aweight average molecular weight (Mw) of 10,000 to 1,000,000; a molecularweight distribution (Mw/Mn) of 1 to 10; and a density of 0.850 to 0.920g/ml.